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WO2016200401A1 - Composés d'alignement - Google Patents

Composés d'alignement Download PDF

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Publication number
WO2016200401A1
WO2016200401A1 PCT/US2015/035546 US2015035546W WO2016200401A1 WO 2016200401 A1 WO2016200401 A1 WO 2016200401A1 US 2015035546 W US2015035546 W US 2015035546W WO 2016200401 A1 WO2016200401 A1 WO 2016200401A1
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WIPO (PCT)
Prior art keywords
group
independently
substituted
divalent
hydrocarbyl
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Ceased
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PCT/US2015/035546
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English (en)
Inventor
Anil Kumar
Ryan STAYSHICH
Meng He
Gobinda Saha
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Transitions Optical Inc
Original Assignee
Transitions Optical Inc
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=53524946&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2016200401(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Transitions Optical Inc filed Critical Transitions Optical Inc
Priority to EP15734754.3A priority Critical patent/EP3307798B2/fr
Priority to CN201580080846.3A priority patent/CN107743485B/zh
Priority to US15/573,212 priority patent/US10875833B2/en
Priority to PCT/US2015/035546 priority patent/WO2016200401A1/fr
Publication of WO2016200401A1 publication Critical patent/WO2016200401A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D263/57—Aryl or substituted aryl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/56—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents

Definitions

  • the present invention relates to compounds that have alignment properties, such as photoalignment properties, which can be used to prepare alignment materials, such as polymers.
  • Liquid crystal materials are used in various applications.
  • the liquid crystal materials are formed as a layer over the surface of a substrate, such as an ophthalmic lens.
  • the liquid crystal materials of the liquid crystal containing layer are typically orientated or aligned along a common direction. Alignment of the liquid crystal materials can be achieved by contact of the liquid crystal containing layer with an underlying alignment layer. Orientation of the alignment layer can be achieved by physical methods, such as rubbing, and/or remote methods, such as exposure to electromagnetic radiation.
  • Alignment of the alignment layer and correspondingly the liquid crystal materials of the liquid crystal containing layer by remote methods, such as by exposure to electromagnetic radiation, can be desirable compared to physical methods.
  • Physical alignment methods can have associated therewith disadvantages, such as dirt pickup by and/or corruption, such as tearing, of the alignment layer.
  • Remote alignment methods are generally not subject to such disadvantages, and can be advantageously used to define distinct areas across the alignment layer having different alignment directions.
  • Ring-A is selected from the group consisting of aryl and heteroaryl; E is N or C-R 1 ; and D is selected from the group consisting of O, S, and N-R 2 .
  • L 1 and L 4 are each independently selected from at least one of: a single
  • L 2 independently for each m, and L 5 independently for each q are in each case independently selected from the group consisting of divalent linear or branched C1-C25 alkyl, divalent interrupted linear or branched C1-C25 alkyl, divalent linear or branched C1-C25 perhaloalkyl, divalent interrupted linear or branched C1-C25 perhaloalkyl, divalent linear or branched C2-C25 alkenyl, and divalent interrupted linear or branched C2-C25 alkenyl, wherein each divalent interrupted linear or branched C1-C25 alkyl, each divalent interrupted linear or branched C1-C25 perhaloalkyl, and each divalent interrupted linear or branched C2-C25 alkenyl are each independently interrupted with at least one interrupting group selected from the group consisting of -0-, -S-, -C(O)-, -C(0)0-, -OC(0)0-, -
  • Y is, independently for each p and independently for each r, a divalent linking group selected from the group consisting of a single bond, -0-, -S-, -C(O)-, -C(0)0-, -OC(0)0-, -S(O)-, -SO2- , -N(R 9 )-, -N(R 9 )-C(0)-0-, -C(0)-N(R 9 )-, and -Si(R 9 )(R 10 )- wherein R 9 and R 10 are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl.
  • each p and each r independently, for each p and each r, 0 to 5, provided that the sum of v and u is at least 1 for each p that is greater than zero and each r that is greater than zero.
  • Z is, independently for each v, a divalent linking group selected from the group consisting of a single bond, -0-, -S-, -C(O)-, -C(0)0-, -OC(0)0-, -S(O)-, -SO2-, -N(R 9 )-, -N(R 9 )- C(0)-0-, -C(0)-N(R 9 )-, and -Si(R 9 )(R 10 )- wherein R 9 and R 10 are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl.
  • E 1 and E 2 are each independently selected, for each v and each u, from the group consisting of divalent aryl, substituted divalent aryl, divalent heteroaryl, substituted divalent heteroaryl, divalent cycloalkyl, substituted divalent cycloalkyl, divalent heterocycloalkyl, and substituted divalent heterocycloalkyl.
  • each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl are each independently interrupted with at least one interrupting group selected from the group consisting of -0-, -S-, -C(O)- , -C(0)0-, -OC(0)0-, -S(O)-, -SO2-, -N(R 9 )-, and -Si(R 9 )(R 10 )- wherein R 9 and R 10 are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof.
  • E 1 and E 2 of Formula (I) there is the proviso that at least one of E 1 and E 2 independently is, or is independently substituted with, at least one reactive group selected from the group consisting of (linear or branched C-i-Cs alkyl)acryloyl, unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl, thiol, amine, isocyanate, aldehyde, and
  • each direct L 2 -L 3 link between each directly linked L 2 and L 3 is free of two heteroatoms linked together.
  • a direct L 4 -L 5 link between L 4 and L 5 is free of two heteroatoms linked together; a direct L 4 -L 6 link between L 4 and L 6 is free of two heteroatoms linked together; and each direct L 5 -L 6 link between each directly linked L 5 and L 6 is free of two heteroatoms linked together.
  • any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10 that is, all subranges or subratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as but not limited to, 1 to 6.1 , 3.5 to 7.8, and 5.5 to 10.
  • linking groups such as divalent linking groups
  • other appropriate orientations such as, but not limited to, right-to- left orientations.
  • C(0)0- is inclusive of the right-to-left representation thereof
  • molecular weight values of polymers such as weight average molecular weights (Mw) and number average molecular weights (Mn) are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.
  • polydispersity index (PDI) values represent a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/Mn).
  • polymer means homopolymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers.
  • the compounds of the present invention are also referred to herein as alignment compounds and/or alignment monomers.
  • actinic radiation means electromagnetic radiation that is capable of causing a response in a material, such as, but not limited to, transforming compounds according to the present invention, and/or materials prepared therefrom, from a non-aligned arrangement to an aligned arrangement.
  • photochromic and similar terms, such as “photochromic compound” means having an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation.
  • photochromic material means any substance that is adapted to display photochromic properties (such as, adapted to have an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation) and which includes at least one photochromic compound.
  • photochromic material includes thermally reversible photochromic materials and compounds and non-thermally reversible photochromic materials and compounds.
  • thermally reversible photochromic compounds/materials as used herein means compounds/materials capable of converting from a first state, for example a "clear state,” to a second state, for example a "colored state,” in response to actinic radiation, and reverting back to the first state in response to thermal energy.
  • non-thermally reversible photochromic compounds/materials as used herein means compounds/materials capable of converting from a first state, for example a "clear state,” to a second state, for example a "colored state,” in response to actinic radiation, and reverting back to the first state in response to thermal energy.
  • compounds/materials as used herein means compounds/materials capable of converting from a first state, for example a "clear state,” to a second state, for example a "colored state,” in response to actinic radiation, and reverting back to the first state in response to actinic radiation of substantially the same wavelength(s) as the absorption(s) of the colored state (e.g., discontinuing exposure to such actinic radiation).
  • the terms “first” and “second” are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties.
  • the first state and the second state of a photochromic compound can differ with respect to at least one optical property, such as but not limited to the absorption of visible and/or UV radiation.
  • the photochromic compounds of the present invention can have a different absorption spectrum in each of the first and second state.
  • a photochromic compound of the present invention can be clear in the first state and colored in the second state.
  • a photochromic compound of the present invention can have a first color in the first state and a second color in the second state.
  • optical article or element or device means pertaining to or associated with light and/or vision.
  • the optical article or element or device can be chosen from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements and devices.
  • ophthalmic means pertaining to or associated with the eye and vision.
  • ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non- segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact lenses, intra-ocular lenses, magnifying lenses, and protective lenses or visors.
  • display means the visible or machine- readable representation of information in words, numbers, symbols, designs or drawings.
  • Non-limiting examples of display elements include screens, monitors, and security elements, such as security marks.
  • window means an aperture adapted to permit the transmission of radiation there-through.
  • windows include automotive and aircraft transparencies, windshields, filters, shutters, and optical switches.
  • mirror means a surface that specularly reflects a large fraction of incident light.
  • liquid crystal cell refers to a structure containing a liquid crystal material that is capable of being ordered.
  • a non- limiting example of a liquid crystal cell element is a liquid crystal display.
  • the term “mesogen” and similar terms, such as “mesogen group,” “mesogenic,” and “mesogenic group,” means the fundamental unit (or segment or group) of a liquid crystal material that induces, and/or is induced into, structural order amongst and between liquid crystals, such as (but not limited to) liquid crystal materials that are together present in a liquid crystal composition.
  • the terms “formed over,” “deposited over,” “provided over,” “applied over,” residing over,” or “positioned over,” mean formed, deposited, provided, applied, residing, or positioned on but not necessarily in direct (or abutting) contact with the underlying element, or surface of the underlying element.
  • a layer “positioned over” a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.
  • a bond such as used with, but not limited to, L 1 , L 4 , Y, and Z, means a single bond.
  • linear or branched groups such as linear or branched alkyl
  • linear or branched alkyl are herein understood to include: a methylene group or a methyl group; groups that are linear, such as linear C2-C20 alkyl groups; and groups that are appropriately branched, such as branched C3-C20 alkyl groups.
  • heterocycloalkyl group, aryl group, and/or heteroaryl group in which at least one hydrogen thereof has been optionally replaced or substituted with a group that is other than hydrogen, such as, but not limited to, halo groups (e.g., F, CI, I, and Br), hydroxyl groups, ether groups, thiol groups, thio ether groups, carboxylic acid groups, carboxylic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyl groups (including, but not limited to: alkyl; alkenyl; alkynyl; cycloalkyl, including poly-fused-ring cycloalkyl and polycyclocalkyl; heterocycloalkyl; aryl, including hydroxyl substituted aryl, such as phenol, and including poly-fused-ring aryl; heteroaryl, including poly- fused-
  • Rn ' and R12' are each independently selected, with some embodiments, from hydrogen, linear or branched C1-C20 alkyl, C3-C12 cycloakyl, C3-C12 heterocycloalkyl, aryl, and heteroaryl.
  • halo substituted and related terms (such as, but not limited to, haloalkyl groups, haloalkenyl groups, haloalkynyl groups, haloaryl groups and halo-heteroaryl groups) means a group in which at least one, and up to and including all of the available hydrogen groups thereof is substituted with a halo group.
  • halo-substituted is inclusive of "perhalo-substituted.”
  • perhalo- substituted group and related terms such as, but not limited to perhaloalkyl groups, perhaloalkenyl groups, perhaloalkynyl groups, perhaloaryl groups and perhalo-heteroaryl groups
  • perhalomethyl is -CX3
  • perhalophenyl is -CeXs, where X represents one or more halo groups, such as, but not limited to F.
  • the compounds of the present invention include groups and sub-groups that can in each case be independently selected from hydrocarbyl and/or substituted hydrocarbyl.
  • hydrocarbyl and similar terms, such as “hydrocarbyl substituent,” means: linear or branched C1-C25 alkyl (e.g., linear or branched C1-C10 alkyl); linear or branched C2-C25 alkenyl (e.g., linear or branched C2-C10 alkenyl); linear or branched C2-C25 alkynyl (e.g., linear or branched C2-C10 alkynyl); C3-C12 cycloalkyl (e.g., C3-C10 cycloalkyl); C3-C12 heterocycloalkyl (having at least one hetero atom in the cyclic ring); C5-C18 aryl (including polycyclic aryl groups) (e.g., C5-
  • Representative alkyl groups include but are not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl.
  • Representative alkenyl groups include but are not limited to vinyl, allyl and propenyl.
  • Representative alkynyl groups include but are not limited to ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, and 2- butynyl.
  • Representative cycloalkyl groups include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents.
  • Representative heterocycloalkyl groups include but are not limited to imidazolyl, tetrahydrofuranyl, tetrahydropyranyl and piperidinyl.
  • Representative aryl groups include but are not limited to phenyl, naphthyl, anthracynyl and triptycenyl.
  • Representative heteroaryl groups include but are not limited to furanyl, pyranyl, pyridinyl, isoquinoline, and pyrimidinyl.
  • Representative aralkyl groups include but are not limited to benzyl, and phenethyl.
  • substituted hydrocarbyl as used herein means a hydrocarbyl group in which at least one hydrogen thereof has been
  • a group that is other than hydrogen such as, but not limited to, halo groups, hydroxyl groups, ether groups, thiol groups, thio ether groups, carboxylic acid groups, carboxylic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyl groups (e.g., alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl groups), and amine groups, such as -N(Rn')(Ri2') where Rn' and R12' are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl.
  • hydrocarbyl groups e.g., alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and
  • substituted hydrocarbyl is inclusive of halohydrocarbyl (or halo substituted hydrocarbyl) substituents.
  • halohydrocarbyl as used herein, and similar terms, such as halo substituted hydrocarbyl, means that at least one hydrogen atom of the hydrocarbyl (e.g., of the alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl groups) is replaced with a halogen atom selected from chlorine, bromine, fluorine and iodine.
  • the degree of halogenation can range from at least one hydrogen atom but less than all hydrogen atoms being replaced by a halogen atom (e.g., a fluoromethyl group), to full halogenation (perhalogenation) in which all replaceable hydrogen atoms on the hydrocarbyl group have each been replaced by a halogen atom (e.g., trifluoromethyl or perfluoromethyl).
  • a halogen atom e.g., a fluoromethyl group
  • perhalogenation perhalogenation
  • perhalohydrocarbyl group means a hydrocarbyl group in which all replaceable hydrogens have been replaced with a halogen.
  • perhalohydrocarbyl groups include, but are not limited to, perhalogenated phenyl groups and perhalogenated alkyl groups.
  • hydrocarbyl and substituted hydrocarbyl groups from which the various groups described herein can each be independently selected, in some instances and with some embodiments, can in each case be independently interrupted with at least one interrupting group, and when so interrupted are referred to herein as interrupted hydrocarbyl and substituted interrupted hydrocarbyl groups.
  • the interrupted hydrocarbyl and substituted interrupted hydrocarbyl groups can be interrupted with two or more of the above recited linking groups, which can be adjacent to each other or separated by one or more carbons.
  • a combination of adjacent -C(O)- and - N(Rii')- can provide a divalent amide linking or interrupting
  • a combination of adjacent -N(Rn')-, -C(O)- and -O- can provide a divalent carbamate (or urethane) linking or interrupting group, -N(Rn')-C(0)-0-, where R11 ' is hydrogen.
  • the R 1 interrupted hydrocarbyl group can be interrupted with one or more of the above recited divalent interrupting groups, such as but not limited to -0-: (i) along the hydrocarbyl chain thereof; and/or (ii) at the point where R 1 is bonded to the C of C-R 1 .
  • alkyl means linear or branched alkyl, such as but not limited to, linear or branched C1-C25 alkyl, or linear or branched C1-C10 alkyl, or linear or branched C2-C10 alkyl.
  • alkyl groups from which the various alkyl groups of the present invention can be selected from include, but are not limited to, those recited previously herein.
  • cycloalkyi as used herein, in accordance with some embodiments, means groups that are appropriately cyclic, such as but not limited to, C3-C12 cycloalkyi (including, but not limited to, cyclic C5-C7 alkyl) groups. Examples of cycloalkyi groups include, but are not limited to, those recited previously herein.
  • cycloalkyi as used herein in accordance with some embodiments also includes: bridged ring polycycloalkyl groups (or bridged ring polycyclic alkyl groups), such as but not limited to,
  • heterocycloalkyi as used herein, in accordance with some embodiments, means groups that are appropriately cyclic, such as but not limited to, C3-C12 heterocycloalkyi groups or C5-C7 heterocycloalkyi groups, and which have at least one hetero atom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof.
  • heterocycloalkyi groups include, but are not limited to, those recited previously herein.
  • heterocycloalkyi also includes: bridged ring polycyclic heterocycloalkyl groups, such as but not limited to, 7-oxabicyclo[2.2.1 ]heptanyl; and fused ring polycyclic heterocycloalkyl groups, such as but not limited to,
  • heteroaryl in accordance with some embodiments, includes but is not limited to C5-C18 heteroaryl, such as but not limited to C5-C10 heteroaryl (including fused ring polycyclic heteroaryl groups) and means an aryl group having at least one hetero atom in the aromatic ring, or in at least one aromatic ring in the case of a fused ring polycyclic heteroaryl group.
  • heteroaryl groups include, but are not limited to, those recited previously herein.
  • fused ring polycyclic-aryl-alkyl group and similar terms such as, fused ring polycyclic-alkyl-aryl group, fused ring polycyclo-aryl-alkyl group, and fused ring polycyclo-alkyl-aryl group means a fused ring polycyclic group that includes at least one aryl ring and at least one cycloalkyl ring that are fused together to form a fused ring structure.
  • fused ring polycyclic-aryl- alkyl groups include, but are not limited to indenyl, 9H-flourenyl,
  • aralkyl includes but is not limited to C6-C24 aralkyl, such as but not limited to Ce-C-io aralkyl, and means an aryl group substituted with an alkyl group.
  • aralkyl groups include, but are not limited to, those recited previously herein.
  • Ring-A is aryl; and R 1 of E and R 2 of D are each independently selected from hydrogen, linear or branched C1-C25 alkyl, linear or branched C2-C25 alkenyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, aryl, and heteroaryl.
  • m is at least 1 for at least one t; q is at least 1 for at least one s.
  • L 2 is, independently for each m
  • L 5 is, independently for each q, in each case independently selected from divalent linear or branched C1-C25 alkyl, divalent interrupted linear or branched C1-C25 alkyl, divalent linear or branched C1-C25 perhaloalkyi, and divalent interrupted linear or branched Ci- C25 perhaloalkyi, where each divalent interrupted linear or branched C1-C25 alkyl and each divalent interrupted linear or branched C1-C25 perhaloalkyi are each independently interrupted with at least one interrupting group selected from the interrupting groups -0-, -C(0)0-, and -OC(0)0-.
  • L 3 independently for each p, and L 6 independently for each r, are in each case independently represented by the following Formula (II-2), -2)
  • E 1 and E 2 are each independently selected from hydrogen, linear or branched C1-C25 alkyl, interrupted linear or branched C1-C25 alkyl, linear or branched C2-C25 alkenyl, and interrupted linear or branched C2-C25 alkenyl, wherein each interrupted linear or branched C1-C25 alkyl and each interrupted linear or branched C2-C25 alkenyl are each independently interrupted with at least one interrupting group selected from -0-, -S-, and -C(0)0-.
  • E 1 and E 2 of Formula (I) there is the further proviso, with some embodiments, that E 1 and/or E 2 independently is, or is
  • Ring-A of Formula (I) is phenyl, and the monomer represented by Formula (I) is further represented by the following Formula (l-A):
  • R 1 of E and R 2 of D are each independently selected from hydrogen and linear or branched C1-C10 alkyl.
  • L 2 is, independently for each m
  • L 5 is, independently for each q, in each case independently selected from divalent linear or branched C1-C10 alkyl, divalent interrupted linear or branched C1-C10 alkyl, divalent linear or branched C1-C10 perfluoroalkyl, and divalent interrupted linear or branched Ci- C10 perfluoroalkyl, where each divalent interrupted linear or branched C1-C10 alkyl and each divalent interrupted linear or branched C1-C10 perfluoroalkyl are each independently interrupted with at least one interrupting group selected from -0-, -C(0)0-, and -OC(0)0-.
  • Formula (l-A), independently for each L 3 , and independently for each L 6 , Z is, independently for each v, selected from the group consisting of a single bond, -O- and -C(0)0-.
  • phenylen-1 ,4- diyl substituted phenylen-1 ,4-diyl, cyclohexan-1 ,4-diyl, and substituted cyclohexan-1 ,4-diyl.
  • E 1 and E 2 are each independently selected from hydrogen, linear or branched C1-C10 alkyl, and interrupted linear or branched C1-C10 alkyl, where each interrupted linear or branched C1-C10 alkyl is independently interrupted with at least one
  • (meth)acryloyl unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl, thiol, and combinations thereof.
  • each interrupted linear or branched C1-C10 alkyl is independently interrupted with at least one
  • E 1 and E 2 of Formula (I), and correspondingly Formula (l-A) there is the further proviso, with some embodiments, at least one of E 1 and E 2 independently is, or is independently substituted with, (meth)acryloyl.
  • each of E 1 and E 2 independently is, or is independently substituted with, at least one reactive group, which can be selected from those classes and examples of reactive groups recited previously herein.
  • E 1 is, or is substituted with, a reactive group selected from the group consisting of oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, and isocyanate; and
  • E 2 is, or is substituted with, a reactive group selected from the group consisting of hydroxyl, thiol, and amine.
  • each E 1 and each E 2 are in each case independently represented by the following Formula (VII), (VII)
  • L * is selected from a bond, such as a single bond, multivalent hydrocarbyl, multivalent substituted hydrocarbyl, multivalent interrupted hydrocarbyl, and multivalent substituted interrupted hydrocarbyl, where each multivalent interrupted hydrocarbyl and each multivalent substituted interrupted hydrocarbyl are each independently interrupted with at least one interrupting group selected from -0-, -S-, -C(O)- , -C(0)0-, -OC(0)0-, -S(O)-, -SO2-, -N(R 9 )-, and -Si(R 9 )(R 10 )- where R 9 and R 10 are each independently selected from hydrogen, hydrocarbyl, and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof.
  • n in each case is independently at least 1 , such as 1 to 10, or 1 to 8, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 2, or 1.
  • X * in each case and independently for each n is a reactive group selected from (linear or branched C-i-Cs alkyl)acryloyl, unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl, thiol, amine, isocyanate, aldehyde, and combinations thereof.
  • X * in each case and independently for each n is a reactive group selected from (linear or branched C-i-Cs alkyl)acryloyl, unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid este
  • the compounds of the present invention can be used alone or can be used to prepare other materials, such as polymers.
  • the compounds of the present invention can be referred to as monomers, or monomer compounds, and polymers prepared therefrom include residues of such monomers or monomer compounds of the present invention.
  • polymers prepared from one or more compounds of the present invention, such as represented by Formula (I) further include at least one residue of an additional monomer selected from (meth)acrylic acid, hydrocarbyl (meth)acrylate, substituted hydrocarbyl (meth)acrylate, unsubstituted styrene, substituted styrene, and combinations thereof.
  • D is O.
  • L 1 and L 4 are each independently selected from t one of the following Formulas Ilia, lllb, lllc, llld, llle, or lllf:
  • R 7 is selected from hydrocarbyl and substituted hydrocarbyl
  • R 8 is selected from hydrocarbyl and substituted hydrocarbyl, o
  • R b is selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and O
  • R c and R d are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl.
  • R 7 and R 8 for each of L 1 and L 4 are each independently selected from divalent linear or branched C1-C25 alkyl, divalent linear or branched C2-C25 alkenyl, divalent C3-C12 cycloalkyl, divalent C3-C12 heterocycloalkyl, divalent aryl, and divalent heteroaryl.
  • L 1 and L 4 of Formula (I) are each independently the divalent linking group represented by Formula 11 Id, and each R 8 is independently a divalent linear or branched C-i-Cs alkyl group.
  • R b , R c , and R d for each of L 1 and L 4 are each independently selected from linear or branched C1-C25 alkyl, linear or branched C2-C25 alkenyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, aryl, and heteroaryl.
  • R b , R c , and R d for each of L 1 and L 4 are each independently a linear or branched C-i-Cs alkyl group.
  • divalent Ring-(B) and divalent Ring-(C) are each independently selected from the group consisting of divalent aryl, substituted divalent aryl, divalent heteroaryl, and substituted divalent heteroaryl.
  • divalent Ring-(B) and divalent Ring-(C) are each independently selected from the group consisting of phenylen-1 ,4-diyl, substituted phenylen-1 ,4-diyl, pyrimidin- 2,5-diyl, substituted pyrimidin-2,5-diyl, pyridine-2,5-diyl, substituted pyridine- 2,5-diyl, naphthalene-2,6-diyl, substituted naphthalene-2,6-diyl, and phenanthrene-2,7-diyl.
  • each L 3 and each L 6 are in each case independently a divalent group selected from the following Formulas, IV(A) through IV(O):
  • At least one of L 3 and L 6 independently is a mesogenic group, and the compound is a mesogenic compound.
  • Polymers prepared from the mesogenic compounds of the present invention, such as represented by Formula (I), can have mesogenic properties, and
  • mesogenic polymers correspondingly are mesogenic polymers. Since the polymers that include at least one residue of at least one compound represented by Formula (I), and at least one of L 3 and L 6 independently is a mesogenic group, such polymers can be described as mesogenic polymers when at least one of L 3 and L 6 independently is a mesogenic group.
  • Non-limiting examples of compounds according to the present invention include those represented by the following Formulas (M-1 ) to (M-17):
  • t' is from 1 to 4; L 1 , L 2 , and L 3 , are each independently as described previously herein with reference to Formula (I); m is, independently for each t', from 0 to 4; p is, independently for each t', from 0 to 4, provided that the sum of m and p is at least one for each t'.
  • E 3 and E 4 are each
  • each interrupted hydrocarbyl and each substituted interrupted hydrocarbyl are each independently interrupted with at least one interrupting group selected from -0-, -S-, -C(O)-, -C(0)0-, -OC(0)0-, -S(O)-, -SO2-, -N(R 9 )-,
  • R 9 and R 10 are each independently selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more interrupting groups thereof.
  • E 3 is, or is substituted with, at least one reactive group selected from (linear or branched C-i-Cs alkyl)acryloyl, unsubstituted styrene, substituted styrene, oxirane, thiirane, carboxylic acid, carboxylic acid ester, unsubstituted cyclic carboxylic acid ester, substituted cyclic carboxylic acid ester, cyclic carboxylic acid anhydride, hydroxyl, thiol, amine, isocyanate, aldehyde, and
  • E 3 of Formula (V) is independently represented by Formula (VII) as described previously and independently herein with regard to E 1 and E 2 of Formula (I).
  • Polymers prepared from the compounds of the present invention include at least one polymer segment represented by the following Formula (VI),
  • E 1a independently for each x is a divalent residue of E 1 of Formula (I):
  • E 2a independently for each y is a divalent residue of E 2 of Formula (I); and
  • E 3a independently for each z is a divalent residue of E 3 of Formula (V).
  • h is from 1 to 10,000; x is from 0 to 10 for each h; y is from 0 to 10 for each h; and z is from 0 to 10 for each h.
  • Polymers prepared from the compounds of the present invention can, with some embodiments, be selected from linear polymers, branched polymers, star polymers, graft polymers, and mixtures thereof.
  • chain architecture independently have a chain architecture (or chain structure) selected from: random chain architecture (in which the monomer residues are distributed randomly along the polymer segment); block chain architecture (in which the monomer residues are distributed in blocks along the polymer segment);
  • E 1a , E 2a , and E 3a are each independently a residue of a radically polymerizable group, and at least the polymer segment represented by Formula (VI) is prepared by art-recognized radical polymerization methods, such as, but not limited to, free radical polymerization methods, and living radical polymerization methods, such as atom transfer radical polymerization methods.
  • E 1a , E 2a , and E 3a are each independently a residue of a (meth)acryloyl group.
  • Polymers prepared from the compounds of the present invention include at least one polymer chain segment represented by Formula (VI) as described above.
  • the polymer chain segment represented by Formula (VI) can represent one or more segments that form (or define) at least a portion of the chain, or backbone, architecture of the polymer.
  • the polymer chain segment represented by Formula (VI) is located in at least one of: the backbone of the polymer; one or more branches of the polymer (when the polymer is branched); and one or more arms of the polymer (when the polymer has star or comb architecture).
  • polymers prepared from the compounds of the present invention include at least one polymer chain segment represented by Formula (VI), such as 1 to 100, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 1 to 5, or 1 to 3 polymer chain segments represented by Formula (VI).
  • Polymers prepared from the compounds of the present invention can have any suitable molecular weight. With some embodiments, such polymers have a Mw of from 5,000 to
  • the compounds of the present invention such as represented by Formula (I), and/or polymers prepared from such compounds can be used to form or as one or more components of an alignment layer.
  • the term “alignment layer” means a layer that can facilitate the positioning of one or more other structures that are exposed, directly and/or indirectly, to at least a portion thereof.
  • the term “order” means bringing into a suitable arrangement or position, such as aligning with another structure or material, or by some other force or effect.
  • the term “order” encompasses both: (i) contact methods of ordering a material, such as by aligning with another structure or material; and (ii) non-contact methods of ordering a material, such as by exposure to an external force or effect.
  • order also encompasses combinations of contact and non-contact methods.
  • liquid crystal materials, dichroic compounds, and/or photochromic-dichroic compounds that are at least partially aligned by interaction with the alignment layer can be at least partially aligned such that the long-axis of the liquid crystal materials, dichroic compounds, and/or photochromic-dichroic compounds (such as in an activated state) are essentially parallel to at least the first general direction of the alignment layer.
  • the liquid crystal materials, dichroic compounds, and/or photochromic-dichroic compounds that are at least partially aligned by interaction with the alignment layer are bound to or reacted with the alignment layer.
  • general direction refers to the predominant arrangement or orientation of the material, compound or structure. Further, it will be appreciated by those skilled in the art that a material, compound or structure can have a general direction even though there is some variation within the arrangement of the material, compound or structure, provided that the material, compound or structure has at least one predominate arrangement.
  • Alignment layers that include one or more compounds of the present invention, such as represented by Formula (I), and/or polymers prepared from such compounds, can, with some embodiments, have at least a first general direction.
  • the alignment layer can include a first ordered region having a first general direction and at least one second ordered region adjacent the first ordered region having a second general direction that is different from the first general direction.
  • the alignment layer can have a plurality of regions, each of which has a general direction that is the same or different from the remaining regions so as to form a desired pattern or design.
  • Alignment layers that include the compound(s) of the present invention and/or polymer(s) prepared from such compounds, can, with some embodiments, be crosslinked alignment layers, non-crosslinked alignment layers (such as, but not limited to, a thermoplastic alignment layer), and combinations thereof.
  • the alignment layer can be in the form of a film (such as formed from a thermoplastic coating composition and/or a crosslinkable coating composition), a sheet (such as formed by extrusion of a thermoplastic extrusion composition and/or a crosslinkable extrusion composition), and combinations thereof.
  • Alignment layers that include one or more compounds of the present invention and/or polymer(s) prepared from such compound(s), can be aligned by art-recognized methods including, but not limited to, contact methods (such as by a shear force), and non-contact methods (such as by exposure to a magnetic field, an electric field, and/or linearly polarized radiation).
  • the alignment layer is in the form of a sheet, which can be aligned by uniaxial stretching and/or during extrusion of the sheet.
  • Alignment layers that include one or more compounds of the present invention and/or polymer(s) prepared from such compound(s), can be used in conjunction with an optical element, which includes: an optical substrate; and in which the alignment layer resides over at least a portion of a surface of the optical substrate.
  • the alignment layer of the optical element is at least partially aligned by exposing at least a portion of the alignment layer to at least one of, a magnetic field, an electric field, linearly polarized radiation, and shear force, in each case in accordance with art-recognized methods.
  • the optical element is selected from an ophthalmic element, a display element, a window, a mirror, and a liquid crystal cell element.
  • optical element is an optical element
  • ophthalmic element which is selected from a corrective lens, a non-corrective lens, a contact lens, an intra-ocular lens, a magnifying lens, a protective lens, and a visor.
  • the optical element includes over at least a portion of the surface of the optical substrate, at least one additional layer, where each additional layer is independently selected from a primer layer, a protective layer, an anti-reflective layer, a reflective layer, a polarizing layer, a photochromic layer, a liquid crystal layer, and combinations thereof.
  • the primer layer, protective layer, anti-reflective layer, reflective layer, polarizing layer, photochromic layer, and liquid crystal layer can in each case be selected from art-recognized classes and examples of each such layers.
  • Each optional photochromic layer of the optical element includes one or more art-recognized photochromic compounds and/or photochromic- dichroic compounds.
  • Classes of photochromic compounds that can be included in each optional photochromic layer include, but are not limited to, indeno-fused naphthopyrans, naphtho[1 ,2-b]pyrans, naphtho[2,1 -b]pyrans, spirofluoroeno[1 ,2-b]pyrans, phenanthropyrans, quinolinopyrans,
  • fluoroanthenopyrans spiropyrans, benzoxazines, naphthoxazines,
  • photochromic layer of the optical element include, or can be, with some embodiments, photochromic-dichroic materials and compounds.
  • the photochromic-dichroic materials and compounds can, with some embodiments, photochromic-dichroic materials and compounds.
  • the photochromic-dichroic materials and compounds can, with some embodiments, photochromic-dichroic materials and compounds.
  • Photochromic-dichroic compounds typically have a photochromic group (P) and at least one lengthening agent or group (L) covalently bonded to the photochromic group.
  • the photochromic groups of the photochromic-dichroic compounds can be selected from those classes and examples as described previously herein with regard to the photochromic compounds, such as, but not limited to, pyrans, oxazines, fulgides, and indeno-fused naphthopyrans.
  • Examples of photochromic-dichroic compounds that can be included in the photochromic layer of the optical elements include, but are not limited to those disclosed in United States Patent No.
  • lengthening groups (L) and photochromic groups (P) include, but are not limited to those disclosed in United States Patent No. 7,256,921 B2 at column 22, line 47 through column 35, line 27, which disclosure is incorporated herein by reference.
  • the photochromic compounds and/or photochromic-dichroic compounds can be present in the photochromic layer, in amounts (or ratios) such that the resulting photochromic layer (and the coated optical element) exhibits desired optical properties.
  • the amount and types of photochromic compounds and/or photochromic- dichroic compounds can be selected such that the photochromic layer is clear or colorless when the photochromic compounds and/or photochromic-dichroic compounds are in the closed-form (e.g., in the bleached or unactivated state), and can exhibit a desired resultant color when the photochromic compounds and/or photochromic-dichroic compounds are in the open-form (e.g., when activated by actinic radiation).
  • the precise amount of the photochromic compounds and/or photochromic-dichroic compounds that are utilized is not critical, provided that at least a sufficient amount is used to produce the desired effect.
  • the particular amount of the photochromic compounds and/or photochromic-dichroic compounds used can depend on a variety of factors, such as but not limited to, the absorption characteristics of the photochromic compounds and/or photochromic-dichroic compounds, and the color and intensity of the color desired upon activation.
  • the amount of the photochromic compound(s) and/or photochromic-dichroic compound(s) that are present in the photochromic layer formed over the optical substrate of the optical element can range from 0.01 to 40 weight percent, or from 0.05 to 15, or from 0.1 to 5 weight percent, based on the weight of the photochromic coating layer.
  • two or more photochromic compounds are used in combination with each other and/or with one or more photochromic- dichroic compounds, so as to complement one another and to produce a desired color or hue.
  • mixtures of photochromic compounds can be used with some embodiments to attain certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S. Patent 5,645,767, column 12, line 66 to column 13, line 19, the disclosure of which is specifically incorporated by reference herein, which describes the parameters that define neutral gray and brown colors.
  • the photochromic layer can have any suitable thickness, provided it provides a desirable level of photochromic properties, such as but not limited to a desirable range of optical density values.
  • each photochromic layer independently has a thickness of from 0.5 to 50 microns, such as from 1 to 45 microns, or from 2 to 40 microns, or from 5 to 30 microns, or from 10 to 25 microns.
  • Example 1 Step 1 (0.69 g), 4-((6-(methacryloyloxy)hexyl)oxy)-3- methoxybenzoic acid (1.20 g), dimethylaminopyridine (0.04 g), 3,5-di-tert-4- butylhydroxytoluene (0.10 g) and ⁇ /, ⁇ /'-dicyclohexylcarbodiimide (0.74 g) were dissolved in dichloromethane (20 ml). After 16 hours, the reaction mixture was filtered to remove urea byproduct and the filtrate was concentrated under reduced pressure.
  • Example 2 The procedure of Example 2 was followed, except an equimolar amount of 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid was used in place of 4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid.
  • a colorless solid (4.05 g) was obtained and NMR spectrum was consistent with 4- (benzo[c
  • Example 2 The procedure of Example 2 was followed, except an equimolar amount of 3-fluoro-4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid was used in place of 4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid.
  • a colorless solid (2.49 g) was obtained and NMR spectrum was consistent with 4-(benzo[c
  • Example 2 The procedure of Example 2 was followed, except an equimolar amount of 4-((6-(methacryloyloxy)hexyl)oxy)-3-methylbenzoic acid was used in place of 4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid.
  • a colorless solid (0.61 g) was obtained and NMR spectrum was consistent with 4-(benzo[c
  • Example 7 The procedure of Example 1 , Step 3 was followed, substituting the product of Step 3 above (3.70g) in place of the product of Example 1 , Step 2. A colorless solid (2.60 g) was obtained and NMR spectrum was consistent with 4-(benzo[c
  • Example 7
  • Vanillic acid (8.41 g) and 2-aminophenol (5.46 g) were combined in a 100 mL round bottom flask.
  • Trimethylsilyl polyphosphate (25 ml_) was added neat and the mixture was heated to 180°C for 45 minutes. The black mixture was poured over ice and stirred for 16 hours. The precipitate was filtered and dried to yield a greenish grey powder (10.63 g).
  • NMR spectrum was consistent with 4-(benzo[c ]oxazol-2-yl)-2methoxyphenol.
  • Example 1 The procedure of Example 1 , Steps 2 and 3 were followed, except an equimolar amount of the product of Step 1 above was used in place of the product of Example 1 , Step 2 to yield an off-white solid (2.60 g) intermediate after Step 2.
  • the final product was a colorless solid (1.02 g) with an NMR spectrum consistent with 6-(4-(benzo[c
  • Example 7 The procedure of Example 7, Step 1 was followed, except an equimolar amount of syringic acid was used in place of vanillic acid. A purple powder (10.84 g) was obtained and NMR spectrum was consistent with 4- (benzo[c
  • Example 1 The procedure of Example 1 , Steps 2 and 3 were followed, except an equimolar amount of the product of Step 1 above was used in place of the product of Example 1 , Step 2 to yield a red oil (2.95 g) after Step 2.
  • the final product after Step 3 was an off-white solid (1.79 g) with an NMR spectrum consistent with 6-(4-(benzo[c ]oxazol-2-yl)-2,6-dimethoxyphenoxy)hexyl methacrylate.
  • Example 1 The procedure of Example 1 , Steps 2 and 3 were followed, except an equimolar amount of the product of Step 1 above (2.343g) was used in place of the product of Example 1 , Step 2 to yield a colorless solid (3.23 g) after Step 2.
  • the final product after Step 3 was a colorless solid (2.45 g) with an NMR spectrum consistent with 6-(4-(benzofuran-2-yl)phenoxy)hexyl methacrylate.
  • Example 9 Step 1 (2.50 g), 4-((6-(methacryloyloxy)hexyl)oxy)-3- methoxybenzoic acid (4.40 g), dimethylaminopyridine (0.15 g), 3,5-di-tert-4- butylhydroxytoluene (0.10 g) and ⁇ /, ⁇ /'-dicyclohexylcarbodiimide (2.70 g) were dissolved in dichloromethane (60 ml). After 16 hours, the reaction mixture was filtered to remove urea byproduct and the filtrate was concentrated under reduced pressure.
  • Example 10 The procedure of Example 10 was followed, except an equimolar amount of 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid was used in place of 4-((6-(methacryloyloxy)hexyl)oxy)-3-methoxybenzoic acid.
  • a colorless solid (4.03 g) was obtained with an NMR spectrum consistent with 4-(benzofuran-2- yl)phenyl 4-((6-methacryloyloxy)hexyl)oxy)benzoate.
  • Example 9 The procedure of Example 9, Step 1 was followed, except an equimolar amount of benzo[£>]thiophen-2-ylboronic acid was used in place of benzo[£>]furan-2-ylboronic acid to yield a colorless solid (8.63 g).
  • Example 10 The procedure of Example 10 was followed, except an equimolar amount of the product of Step 1 was used in place of the product of Example 9, Step 1. A colorless solid (3.96 g) was obtained and NMR spectrum was consistent with 4-(benzo[£>]thiophen-2-yl)phenyl 4-((6- (methacryloyloxy)hexyl)oxy)-3-methoxybenzoate.
  • Example 12 Step 1 (2.50 g), 4-((6-(methacryloyloxy)hexyl)oxy)benzoic acid (3.71 g), dimethylaminopyridine (0.13 g), 3,5-di-tert-4-butylhydroxytoluene (0.10 g) and ⁇ /, ⁇ /'-dicyclohexylcarbodiimide (2.50 g) were dissolved in dichloromethane (60 ml). After 16 hours, the reaction mixture was filtered to remove urea byproduct and the filtrate was concentrated under reduced pressure.
  • Example 15 The procedure of Example 15, Step 1 was followed, except the product of Step 1 above (4.5 g) was used in place of the commercially available material to yield a colorless solid (3.82 g) with an NMR spectrum consistent with 2-(4-fluorophenyl)benzo[c
  • Example 13 The procedure of Example 13 was followed, except the product of Example 16, Step 2 (1.0 g) was used in place of the product of Example 12, Step 1.
  • a colorless solid (1.37 g) was obtained having an NMR spectrum that was consistent with 2-(4-fluorophenyl)benzo[d]oxazol-5-yl 4-((6- (methacryloyloxy)hexyl)oxy)benzoate.

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Abstract

La présente invention concerne des composés représentés par la formule (I) suivante. En référence à la Formule (I), au moins un des E1 et E2 est indépendamment, ou est indépendamment substitué par, au moins un groupe réactif, tel qu'un groupe (méth)acryloyle. Les composés selon l'invention peuvent être utilisés seuls et/ou en combinaison avec des polymères préparés à partir de ces composés, de façon à former un ou plusieurs composants d'une couche d'alignement.
PCT/US2015/035546 2015-06-12 2015-06-12 Composés d'alignement Ceased WO2016200401A1 (fr)

Priority Applications (4)

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EP15734754.3A EP3307798B2 (fr) 2015-06-12 2015-06-12 Composés d'alignement
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US15/573,212 US10875833B2 (en) 2015-06-12 2015-06-12 Alignment compounds
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CN107743485B (zh) 2021-10-22
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CN107743485A (zh) 2018-02-27
EP3307798B2 (fr) 2024-06-05
US10875833B2 (en) 2020-12-29
US20180086725A1 (en) 2018-03-29

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